Phenyl-azo-indole compounds

ABSTRACT

Monoazo dyestuffs which in the form of the free acid correspond to the general formula   WHEREIN R1 is hydrogen or alkyl; R2 is hydrogen, halogen, alkyl, alkoxy, nitro, nitrile, carbonamide or carboxylic acid ester; R3 is hydrogen, halogen, alkyl or alkoxy; R4 is alkyl or aryl; R5 is hydrogen or alkyl, R6 is hydrogen, halogen or alkyl; R7 is hydrogen, halogen, alkyl, alkoxy or nitrile; X is C2-C4-alkylene, aralkylene or phenylene; Y is SO3H or, if X is phenylene, SO3H or a radical -SO2-NH-SO2-R8; and R8 is alkyl, aryl or dialkylamine. These dyestuffs are used for the dyeing of natural and synthetic fibre materials, especially for dyeing polyamide fibres. They yield level yellow to orange dyeings with very good fastness to light. Dyestuffs are absorbed well on polyamide fibres even in a neutral to weakly acid dyebath. The dyestuffs are employed in the form of the free acid or in the form of its salts, especially the alkali salts, such as the sodium or potassium salts or the ammonium salts.

United States Patent n 1 Sommer et al.

[ PHENYL-AZO-INDOLE COMPOUNDS [75] Inventors: Richard Sommer; ManfredWiesel;

Hans-Giinter Otten; Edgar Siegel, all of Leverkusen, Germany [73]Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk, Germany [22] Filed: Dec. 1, I972 [2]] Appl. No.:311,414

[30] Foreign Application Priority Data Dec. 2, I971 Germany 2l59802 [52]US. Cl 260/165; 260/319.I; 260/326.l3 R;

260/326.l4 R; 260/326.l5; 260/326.16', 260/507 R; 260/508; 260/509;260/556 SN Primary Examiner-Floyd D. Higel Assistant Examiner-C. F.Warren Attorney, Agent, or Firm-Plumley & Tyner [451 June 24, 1975 57ABSTRACT Monoazo dyestuffs which in the form of the free acid correspondto the general formula Qatar -11, Y-X-N-SO wherein R, is hydrogen oralkyl; R is hydrogen, halogen, alkyl, alkoxy, nitro, nitrile,carbonamide or carboxylic acid ester; R is hydrogen, halogen, alkyl oralkoxy; R is alkyl or aryl; R is hydrogen or alkyl, R is hydrogen,halogen or alkyl; R, is hydrogen, halogen, alkyl, alkoxy or nitrile; Xis C -C -alky1ene, aralkylene or phenylene; Y is SO H or, if X isphenylene, SO H or a radical -SO,--NHSO R and R is alkyl, aryl ordialkylamine. These dyestuffs are used for the dyeing of natural andsynthetic fibre materials, especially for dyeing polyamide fibres. Theyyield level yellow to orange dyeings with very good fastness to light.Dyestuffs are absorbed well on polyamide fibres even in a neutral toweakly acid dyebath. The dyestuffs are employed in the form of the freeacid or in the form of its salts, especially the alkali salts, such asthe sodium or potassium salts or the ammonium salts.

4 Claims, No Drawings 1 v 2 PHENYL-AZO-INDOLE COMPOUNDS alkyleneradicals X are CH CH gH-CH The sub ect of the present invention aremondazo H dyestufis which in the form of the free acid correspond to theformula 5 CH ,-CH -CH -iH-CH CH -GH Illl'l-(ili -GH -CH -(;ll-land -CHCH -CH -CH H3 3 CH3 R7 and CH -CG CH -CH 6 Examples of suitablearalkylene radicals X are ca 2 2" (I l Q 2 Andi N R and g R wherein R 2the benzene ring can optionally be substituted further. Examples ofsuitable phenylene radicals are 12-, in which 1,3- and l,4-phenylene.The phenylene rings of the R, hydrogen or alkyl. aralkylene andphenylene radicals can be substituted R hydrogen, halogen, alkyl,alkoxy, nitro, nitrile, further, for example by alkyl, especially CC,-alkyl, carbonamide or carboxylic acid ester, such as CH,-,, C- ,H,-,and C H or aralkyl, such as R, hydrogen, halogen. alkyl or alkoxy, C.,H-,CH by aryl, especially optionally substituted R, alkyl or aryl phenyl,by alkoxy, especially C,-C,-alkoxy. such as R hydrogen or alkyl, CH;,Oor C H,-,O-, or aralkoxy, such as C,,H,-,CH- R hydrogen, halogen oralkyl, ,-O, by aryloxy, especially optionally substituted R hydrogen,halogen, alkyl, alkoxy or nitrile, phenoxy, and also by chlorine,bromine, nitrile or nitro. X C- C -alkylene, aralkylene or phenylene,Within the framework of the formula (I), preferred Y SO;;H or, if Xphenylene, SO3H or a radical dyestuffs are those which in the form ofthe free acid SO NH-SO R,, correspond to the formula wherein 1 R,,alkyl, aryl or dialkylamine as well as their manua facture and use fordyeing natural and synthetic fibre materials.

I I The alkyl groups preferably contain 1 l2 C atoms Y x l s t and canpossess further subtituents, for example chlo- R. rine, bromine,nitrile, carbamoyl, alkoxy and alkoxycarbfmyl' 40 wherein Suitable alkylgroups R,, R,, R R; and R are, In par- X, Y R1. R2, R31 RM R5, RH and R7have the above ticular, unsubstituted C,-C,-alkyl radicals, such as CH3,C285 iC -;H;, n-C H9 and i-'C4Hg.

Suitable alkyl groups R and R are, in particular, C,C,-alkyl radicals,for example CH C 11 nand iso-C H and n-, sec.- and iso-C,H,. which canbe substituted further, for example by chlorine, bromine, ni-

mentioned meaning.

Particularly preferred dyestuffs are those which in the form of the freeacid correspond to the formula trile, carbamoyl, alkoxy, especially C-C,-alkoxy, and (III) alkoxycarbonyl, especially C,C -alkoxycarbonyl.Suity x.fl 0 5 N18 able halogen radicals are in particular chlorine,brot...

mine and fluorine. s 1

Suitable alkoxy radicals R R and R; are in, particular, those with l 4 Catoms, for example OCH wherein OC H,-,, OC H; and OC H,,. X, Y, R R,,R,-, and R have the abovementioned Suitable alkyl radicals R are inparticular those with meaning, I 4 C atoms which can be furthersubstituted, for ex- R represents hydrogen, chlorine or bromine andample by CN, CONH NH or COOH. such as, R represents chlorine or bromine,especially those for example, CH;,, C H -C=;H -C,H which in the form ofthe free acid correspond to the C H,CN, C- H,CONH C- H,COOCH and formula:i |i 2- 6O Suitable aryl radicals R, are in particular phenyl ornaphthyl radicals which are optionally substituted fur ther, such asphenyl, biphenylyl or naphthyl.

Suitable aryl radicals R are in particular optionally substituted phenylradicals such as phenyl and C C,- ,5 B0, S-X-N-O, 86 N1 1 -lalkylphenyl, especially methylphenyl. 6;- u

Dimethylamino should be mentioned preferably as a suitable dialkylaminogroup R,,. Examples of suitable t-x-v-o, s Qb a,

wherein R R R,-,, Y and X have the abovementioned meaning are diazotisedand combined with coupling components of the general formula wherein R RR and R; have the abovementioned meaning.

Examples of suitable amines of the formula IV are:N-(4-amino-phenyl-sulphonyl)-2-amino-ethanesulphon ic acid, N-methyl-N-(4-amino-phenylsulphonyl)-2-amino-ethane-sulphonic acid, N-propyl-N-(4-amino-phenyl-sulphonyl)-2-amino-ethanesulphonic acid,N-(4-amino-2-chloro-phenylsulphonyl)-2-amino-ethanc-sulphonic acid,N-ethyl-N- (4-amin0-2-chloro-phenyl-sulphonyl)-2-amino-ethanesulphonicacid, N-(4-amino-3-chloro-phenylsulphonyl)-2-amino-ethane-sulphonicacid, N-methyl-N-(4-amino-3-chloro-phenyl-sulphonyl)-2-aminoethane-sulphonic acid,N-ethyl-N-(4'amino-3-chlorophenyl-sulphonyl)-Z-amino-ethane-sulphonicacid, N- (4-amino-2,5-dichloro-phenyl-sulphonyl)-2-aminoethane-sulphonicacid, N-methyl-N-(4-amino-2,5-dichloro-phenyl-sulphonyl)-2amino-ethane-sulphonic acid,N-ethyl-N-(4-amino-2,5-dichloro-phenylsulphonyl)-2-amino-ethane-sulphonicacid, N-propyl- N-( 4-aminc-2,S-dichloro-phenyl-sulphonyl)-2-aminoethane-sulphonic acid,N-(4-amino-3,5-dichlorophenyl-sulphonyl)-Z-amino-ethane-sulphonic acid,N- methyl-N-( 4-amino-3 ,5-dichloro-phenyl-sulphonyl )-2-amino-ethane-sulphonic acid,N-(4-amino-3-methylphenyl-sulphonyl)-Z-amino-ethane-sulphonic acid, N-(4-amino-3-rnethoxy-phenyl-sulphonyl)-2-aminoethane-sulphonic acid,N-methyl-N-(4-amino-3-methoxy-phenyl-sulphonyl)-Z-amino-ethane-sulphonic acid,N-(4-amino-3-ethoxy-phenyl-sulphonyl)-2- amino-ethane-sulphonic acid,N-(4-amino-3- trifiuoromethyl-phenyl-sulphonyl)-2-amino-ethanesulphonicacid, N-methyl-N-(4-amino-3-trifluoromethyl-phenyl-sulphonyl)-2-amino-ethanesulphonic acid,N-propyl-N-(4-amino-3- trifluoromethyl-phenyl-sulphonyl)-2-amino-ethane-4 sulphonic acid, N-(4-amino-phenyi-sulphonyl)-3- amino-propyl-sulphonicacid, N-methyl-N-(4-aminophenyl-sulphonyl)-3-amino-propyI-sulphonicacid, N- (4-amino-2-chloro-phenyI-sulphonyl)-3-amino-propylsulphonicacid,N-ethyl-N-(4-amino-3-chloro-phenylsulphonyl)-3-amino-propyl-sulphonicacid, N-(4-amino-2,5-dichloro-phenyl-sulphonyl)-3-amino-propyl-sulphonic acid,N-methyl-N-(4-amino-2,5-dichloro-phenyl-sulphonyl)-3-amino-propyl-sulphonic acid,N-(4-amino-3,S-dichloro-phenyl-sulphonyl)-3- amino-propyl-sulphonicacid, N-methyl-N-(4-amino-3,5-dichloro-phenyl-sulphonyl)-3-amino-propylsulphonic acid,N-propyl-N-(4-amino-3,5-dichlorophenyl-sulphonyl)-3-amino-propyl-sulphonicacid, N- methyl-N-(4-amin0-3-methyl-phenyl-sulphonyl)-3-amino-propyl-sulphonic acid, N-(4-amino-3-trifluoromethyl-phenyl-sulphonyl)-3-amino-pr0pylsulphonic acid,N-(4-amino-phenyl-sulphonyl)-3- amino-butyI-sulphonicacid,N-(4-amino-2,5-dichlorophenyl-sulphonyl)-3-amino-butyl-sulphonicacid, N- methyl-N-(4amino-2,5-dichloro-phenyl-sulphonyl)-3-amino-butyl-sulphonic acid,N-(4-amino-3,5-dichlorophenyl-sulphonyl)-3-amino-butyl-sulphonic acid,N- methyl-N-(4-amino-3,S-dichloro-phenyl-sulphonyl)-3-amino-butyl-sulphonic acid, N-ethyl-N-(4-amino-3,S-dichloro-phenyl-sulphonyl)-3-amino-butyl-sulphonic acid,N-ethyl-N-(4-amino-3-methyl-phenyl-sulphonyl)- B-amino-butyl-sulphonicacid, N-methyl-N-(4-amino-3-methoxy-phenyl-sulphonyl)-3-amino-butyl-sulphonic acid,N-(4-amino-3-trifluoromethyl-phenyl-sulphonyl)- 3-amino-butyl-sulphonicacid, N-methyl-N-(4-amino-3-trifluoromethyl-phenyl-sulphonyl)-3-amino-butylsulphonic acid,N-(4-amino-phenyl-sulphonyl)-4- amino-butyl-sulphonic acid,N-methyl-N-(4-aminophenyl-sulphonyl)-4-amino-butyl-sulphonic acid, N-(4- amino-2-chloro-phenyl-sulphonyl )-4-amino-butylsulphonic acid,N-(4-amino-3-chloro-phenylsulphonyl)- 4-amino-butyl-sulphonic acid,N-(4-amino- 2,5-dichlorophenyl-sulphonyl)-4-amin0-butylsulphonic acid,N-methyl-N-(4-amino-2,5-dichlorophenyl-sulphonyl)-4-amino-butyl-sulphonicacid, N-(4- amino-3,5-dichloro-phenyl-sulphonyl)-4-amino-butylsulphonicacid,N-(4-amino-3-trifluoromethyl-phenylsulphonyl)-4-amino-butyl-sulphonicacid, N-methyl-N- (4-amino-3-trifluoromethyl-phenyl-sulphonyl)-4-amino-butyl-sulphonic acid,N-(4-amino-phenylsuiphonyl)-3-amino-phenyl-sulphonic acid, N-methyl-N-(4-amino-2-chloro-phenyl-sulphonyl)-3-amino-phenyl-sulphonic acid,N-ethyl-N-(4-amino-3-chlorophenyl-sulphonyl)-3-amino-phenyl-sulphonicacid, N- (4-amino-2,5-dichloro-phenyl-sulphonyl)-3-aminophenyl-sulphonicacid, N-methyl-N-(4-amino-2,S-dichloro-phenyl-sulphonyl)-3-amino-phenyl-sulphonic acid,N-methyl-N-(4-amino-3,S-dichloro-phenylsulphonyl)-3-amino-phenyl-sulphonicacid, N-propyl-N-(4-amino-3.5-dichloro-pl1enyl-sulphonyl-3-aminophenyl-sulphonic acid,N-(4-amino-3-methyl-phenylsulphonyl)-3-amino-phenyl-sulphonic acid,N-(4- amino-3-methoxy-phenyl-sulphonyl)-3-amino-phenylsulphonic acid,N-(4-amino-3-trifluoromethyl-phenylsulphonyl)-3-amino-phenyl-sulphonicacid, N-(4- amino-phenyl-sulphonyl)-4-amino-phenyl-sulphonic acid,N-(4-amino-2-chloro-phenyl-sulphonyl)-4- amino-phenyl-sulphonic acid,N-methyl-N-(4-amino-3- chloro-phenyl-sulphonyl)-4-amino-phenyl-sulphonicacid, N-(4-amino-2,S-dichloro-phenyl-sulphonyl)-4-amino-phenyl-sulphonic acid, N-methyl-N-(4-aminoare obtained analogouslyby reaction of the abovementioned acetylaminobenzenesulphochlorides ornitrobenzenesulphochlorides with the amines of the formula 8 form of thefree acid or in the form of its salts, especially the alkali salts, suchas the sodium or potassium salts or the ammonium salts. The formulaegiven above are those of the free acids.

5 In the examples which follow, parts denote parts by H weight. 8' 2' 2EXAMPLE I 349 parts of N-(4amir1o-2,5-dichloro-phenyllsulphonyll-amino-ethanesulphonic acid are dissolved which are known fromthe literature, followed by splitin 200 parts of water by means ofsodium hydroxide soting Off f the acetyl group reduction of the nilfOlution, at pH 7. 7.0 parts of sodium nitrite are added, P- after coolingto C 30 parts of hydrochloric acid (37% Examples suitable p g Componentsof the strength) are added and diazotisation is carried out for mu Mei y-p y fi l5 l5 minutes at 0 5C. Thereafter a solution of [9.3 'l yLZ-dimeIhYI-iI'IdOIC, 1 parts of Z-phenyl-indole in glacial acetic acidis added f y y Y l -l y f F y -p l y to the clear diazo solution and thecoupling which immdolefi-( p y y P 'P 9 am1demediately starts iscompleted by adding sodium ace- B-( y l-P p acld i 'W' late. Thedyestuff which precipitates, which in the form p py ly fl l y y of thefree acid corresponds to the formula propionic acid,Z-B-naphthyl-indole, 2-p-biphenylylindole, 2,5-dimethyl-indole,2.4-dimethyl-7-methoxyindole, 2-phenyl-5-ethoxy-indole,Z-methyl-S-ethoxy- 1 indole, 2-methyl-5-chloroindole.Z-methyl-fi-chloroindole, Z-methyI-S-nitro-indole, Z-methyI-Scyano- H0:s-Qfi -CH= dill-0; 3 H indole, 2-methyl-7-chloro-indole,2-methyl-5-fluoro- C1 indole, 2-methyl-5-bromo-indole, 2-methyl-5,7- K ldichloro-indole and lB-cyanoethyl-Z,o-dimethylindole.

The dyestuffs according to the invention are suitable is filtered offand dried. It dyes polyamide fibres and for dyeing natural and syntheticfibre materials, espepolyamide fabrics. from a weakly acid or neutralbath, cially for dyeing polyamide fibres. They yield level yelin ayellowish-tinged orange of very good fastness to low to orange dyeingsof good yield and very good fastlight. ness to light. They are absorbedwell on polyamide If the procedure indicated in Example l is followedfibres even in a neutral to weakly acid dyebath. By but the compoundslisted in the table which follows are polyamide fibres there are hereunderstood especially employed as the diazo component and as thecoupling those of synthetic polyamides such as e-polycaprolaccomponent,valuable water-soluble monoazo dyestuffs tam or condensation products ofadipic acid and hexaare again obtained, which dye polyamide in yellow tomethylenediamine. The dyestufi's are employed in the 0 orange light-fastshades.

Table Example Diazo Component Coupling Component 2 l-Methyl-2-phenyl-indole HO;,SCH,CH -NH-O. ,S NH

3 2-Methyl-indole 4 l ,Z-Dimethyl-indole 5 l-B-Cyanoethyl-Z-phenylindole6 2,6-Dimethyl-indole 7 /3( 2 Phenylindolyll propionic acid amide 82-Methyl-5-chIoro-indole 9 2-Methyl-7-chloro-indole l0 H0=,SCH- CHl|\lO- .S lPhenyl-indole l l l-Methyl-Z-phenyl-indole l 2Z-Methyl-indole l 3 l -BCyanoethyl-2-phenylindole Cl 1 42-Methyl-5-chloro-indole HO;,SCH CH -CH=-NHO- -S NH l5 2l-Methyl-Z-phenyl-indole Table Example Diazo Component CouplingComponent Cl 122 CH:zSO- -:O- S- NH 2S.- NH2 Z-Methyl-indole Cl l232Phenyl-indole 1 24 l-B-Cyanoethyl-Z- CH =,-SO, ,N O2S --N -Q2SQ- Nphenyl-indole I25 lMethyl-2-phenylindole Cl 12s CtH" gI-MeIhyI-Z-phenyI-S' H H chloro-indole [2 7 2-Methyl-indole 1282,5-Dimeth l-indole CH" SO2 N OES y 129 Z-Methyl-indole H N-O S NH 1 2Z-Methyl-indole so -N-S 2 H 02 131 1 0 5 NH Z-Phenyl-indole N so H 2 2 H2 CF l 32 HO;,S-CH-,CH N-O:S NH 2 Z-Methyl-indole l 33 Z-Phenyl-indole 134 l 2-Dimethyl-indole l 35 l -Ethyl-2.5-dimethylindole Cl I36HO;.SCH-,-CH:-NO -S 6 NH l-Ethyl-Z-methyl- H 2 indole l 372-Methyl-indole EXAMPLE 138 R Preparation of N-(4-amino-2,5-dichloro- R26 phenylsulphonyl)-arnino-ethane-sulphonic acid.

The diazo component used in Example I is prepared as follows: 130 partsof 2,5-dichloro-4-acetylamino- N=N 5 benzene-sulphochloride areintroduced into 750 parts i 2 of a 15 20% strength aqueous taurinesolution at 0C 5 1 3 4 and the mixture is further stirred for 3 hours at0C and one hour at 80C. Thereafter, concentrated hydrochloric acid isadded in the cold until the product precipitates, and the colourlessproduct is filtered off.

We claim: l. Monoazo dyestuff which in the form of the free acidcorresponds to the formula cyano, carbonamido, C,C -alkoxy, Ct-C -alkyl,or C,C -alkyl substituted by chloro, bromo, cyano,

carbamoyl, C C -alkoxy, or alkoxycarbonyl of 1-4 carbon atoms in thealkoxy portion;

R is hydrogen, chloro, bromo, C C -alkoxy, C -C alkyl. or C -C -alkylsubstituted by chloro, bromo. cyano, carbamoyl, C C -alkoxy, oralkoxycarbonyl of 1-4 carbon atoms in the alkoxy portion;

R is C -C -alkyl, phenyl, biphenylyl, naphthyl;

R is hydrogen, C,C -alkyl, or C C -a|kyl substitued by cyano, amino,carbamoyl, or carboxyl;

R6 is hydrogen, chloro, bromo, or C,C4 alkyl,

R; is hydrogen, chloro, bromo, cyano, C C -alkoxy,

or C -C alkyl;

X is C -C -alkylene, methylenephenyl, ethylenephenyl, phenylene, orphenylene substituted by C C alkyl, benzyl, phenyl, C,C -alkoxy,benzyloxy, chloro, bromo, cyano. or nitro',

Y is -SO ,H, or when X is phenylene or substituted phenylene, Y is SO=;Hor SO NHSO R,,; and

R is C C,-alkyl, phenyl, dimethylamino or C -C alkylphenyl.

2. Monoazo dyestuff of claim 1, which in the form of the free acidcorresponds to the formula wherein R,, R R R,, R,-,, R R;, X and Y havethe meaning mentioned in claim 1. 3. Monoazo dyestuff of claim 1 whichin the form of the free acid corresponds to the formula acid correspondsto the formula R2 ll "Ci 4 I wherein R, and X have the same definitionas given in claim R is hydrogen or chloro;

R,-,' is hydrogen, C,-C -alkyl, or C C -alkyl substituted by amino,cyano, carbonamido, or carboxyl; and

R is hydrogen, chloro, or C,C 'alkyl.

III I Page 1 of 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 3 r 1 D d June 24 1975 RICHARD SOMMER et a1 Inventor(s) It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 59, 'C H CN should be C H CN C H COOCH should be C H C00HColumn 2, line 10, delete "and CH -CG CH -CH Column 2, lines 26-27, "C HCH -0-" should be --C H -CH 0 Column 3, line 6, "32" should be Column 7,line 25, "Z-methyl-Scyano" should be Z-methyl 5-cyano Column 7, line 28,"lP- should be l-B- Column 9, line 22, the last part of the formulashould be C1 Column 13, line 67, the first part of the formula should beno 5 NH- Column 15, line 119, -N-C S- should be -NO S- Column 15, line121, -o s-Q-N- should be -o 's.-N

Page 2 oi 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3,891,619 Dated June 24 1975 Inventor(s) RICHARD SOMMER et 1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 17, line 122, the last part of the formula should be QNH-O SQ -01 Column 17, line 124, -O SNHO S should be Q-NH -O S-.

Column 17, line 128, should be same as above.

Column 17, line 131, Q-NH should be Q-NH- -S0 -SO Column 20, line 20, Rshould be R Signed and Scaled this First Day Of November 1977 [SEAL] Anest:

RUTH C. MASON LUTRELLE F. PARKER Attesu'ng Oflicer Acting Commissionerof Patents and Trademarks

1. MONOAZO DYESTUFF WHICH IN THE FORM OF THE FREE ACID CORRESPONDS TOTHE FORMULA
 2. Monoazo dyestuff of claim 1, which in the form of thefree acid corresponds to the formula
 3. Monoazo dyestuff of claim 1which in the form of the free acid corresponds to the formula
 4. Monoazodyestuff which in the form of the free acid corresponds to the formula